Antisoiling aerosol starch prepared from ethoxylated starch and a fluoroacrylate or fluoroalpha substituted acrylate polymer

ABSTRACT

Aerosol spray starch compositions containing fluoropolymer emulsion in alkaline aqueous medium stabilized by ethoxylated starch.

United States Patent Falivene [73] Assignee: Colgate-Palmolive Company,New York,

221 Filed: Mar. 11,1970

21 Appl.No.: 18,764

[52] U.S.Cl ..260/l7.4 ST, 117/l35.5, 117/139.4, 117/165, 252/89,260/296 F, 260/86.1 R, 260/861 E [51] lm. Cl. ..cosr 45/58 [58] Field ofSearch ..260/l7.4 ST, 29.6 F, 86.1; 117/1355 [56] References CitedUNlTED STATES PATENTS 2,461,139 2/1949 Caldwell "260/234 [4 1 Feb. 22,1972 3,068,187 12/1962 Bolstad et al. ..260/29.6 3,081,296 3/ 1963 Smithet al ..260/23 3.5 3,102,103 8/ 1963 Ahlbrecht et al. ..260/29.63,282,905 1 1/1966 Fasick et a1 ....260/89.5

3,345,318 10/1967 Lindemann et ....260/29.6 3,347,812 10/1967 DeMarco etal. ....260/29.6 3,356,628 12/1967 Smith et al ....260/29.6 3,373,1263/1968 Lehrman et al. ....260/17.4 3,378,609 4/ 1968 Fasick et al..260/890 Primary Examiner-William l-l. Short Assistant Examiner-L. L.Lee

Attorney-Herbert S. Sylvester, Murray M. Grill, Norman Blumenkopf,Ronald S. Cornell, Thomas .I. Corum, Richard N. Miller and Robert L.Stone [57] ABSTRACT Aerosol spray starch compositions containingfluoropolymer emulsion in alkaline aqueous medium stabilized byethoxylated starch.

8 Claims, No Drawings ANTISOILING AEROSOL STARCH PREPARED FROMETHOXYLATED STARCH AND A FLUOROACRYLATE R FLUOROALPHA SUBSTITUTEDACRYLATE POLYMER The present invention relates to improved textilesizing compositions, particularly of the type normally used preparatoryto ironing textiles.

The use of starch as a size and stiffening agent for textile materialsis probably as old as textiles themselves. It is only within the lastseveral decades that the housewife has been offered such a product in analready prepared liquid form for application to the textile beforeironing. Such starching compositions are now available in a variety offorms and among the most popular is an aerosol-type formulation.

It is also known to add to aforesaid starch compositions, antisoilingagents which are both water and oil repellent so as to render thetreated textile resistant to both water and oil borne stains.

It has now been found that the fluoropolymer emulsions are superior soilrepellents but have the disadvantage of being unstable in alkali medium.Emulsifiers have been used to stabilize these emulsions but saidemulsifiers have been found to detract from the ironing and repellencycharacteristics of the spray starch compositions.

Consequently, it has also been found that the use of ethoxylated starchstabilizes the fluoropolymer emulsion in alkali medium, thereby yieldinga superior spray starch product, the starch performing the dual functionof fabric stiffening and as a protective colloid. The presence ofethoxylated starch eliminates the need for emulsifiers, which has theadvantages of undiminished soil repellency, reduction of scorching andsticking to soleplate, simplification of processing and reduction ofmaterial costs.

The preferred form of the compositions of this invention is aself-propelling liquid composition wherein the major carrier liquid iswater and the propellent is a suitable low boiling hydrocarbon orhalogenated hydrocarbon as exemplified by methylchloride,methylenechloride, isobutane and the various chlorinated fluorinatedmethanes, ethanes, and the like, such as dichloro difluoro methane andthe like.

The aerosol composition of this invention may be dispensed from any typeof container inclusive of plastic, glass, metal or combinations thereof,In the use of tin cans, which is the type of container most often used,it has been found that acid emulsions are intolerably corrosive.Consequently, the compositions of the present invention are required tohave a pH of about 9.

The alkaline aqueous compositions of the present invention comprise asthe essential ingredients thereof ethoxylated starch and a thermoplasticfilm-forming fluorocarbon polymer as hereinafter described.

The stiffening and protective colloid component is ethoxylated starchprepared by known ethoxylation processes such as reacting starch with analiphatic alkylene oxide having from two to five carbon atoms. Duringthe ethoxylation process, the average molecular weight of the starchproduct is degraded from about 200,000 to 30-50,000, thereby renderingthe lower molecular weight starch more fluid in solution. Theethoxylated starch is an ether-type starch derivative containing about0.05 to 0.08 mole ethylene oxide (when reacted with ethylene oxide) permole of starch. Any starch may be ethoxylated inclusive of those derivedfrom any vegetable source such as corn, wheat, tapioco, potato, waxymaise, etc. Starch derivatives such as dextrines, hydrolized andoxidized starches or other chemically treated starches which stillretain their essentially amylaceous nature and possess a sufficientnumber of reactive hydroxyl groups to be able to react with the alkyleneoxide in the ethoxylation process are also included. The ethoxylatedstarches are stable, homogenous, hydrated colloidal dispersions readilysoluble in water. The viscosity of aforesaid thermoplastic starchproducts can be varied from very high (low fluidity) to very thin (highfluidity) depending onits desired use. For aerosol dispensing it isdesirable to utilize a thin starch solution.

in addition to its sizing properties, ethoxylated starch functions as aprotective colloid for the fluoropolymer. This is believed to be afunction of the relatively large, hydrophilic molecules of theethoxylated starch which remain in colloidal suspension and coat thefluoropolymer hydrophobic molecules to confer onto them a hydrophilicnature. This protective action maintains the fluoropolymer in suspensionwithout the need for emulsifying agents.

The amount of starch material which may be employed in the compositionsof this invention may be varied widely, but in general from about 1 toabout 10 percent thereof based on the total weight of the aerosolformulation may be used. More important than the specific amount of thestarch, is the ratio of the latter to the fluorocarbon polymer employed.In general the ratio of these two components may vary from about 3:1 tol00: l (starch to fluoropolymer). The minimum ratio of starch tofluoropolymer emulsion containing 22 percent solids is 1.00:1.44 inorder to obtain adequate stabilization of the fluoropolymer. By the useof the aforementioned ratios it has been found that an outstanding,protective and stiffening action is obtained which does not interferewith the provision of excellent soil resistance.

The fluoropolymer component of the compositions of this inventioncomprise a thermoplastic polymeric material in the form of an emulsion,known as a latex, which is characterized by the ability to dry to acontinuous cohesive film. Fluoropolymers are well known but those whichare preferred in the present invention comprise the general class of theperfluoro acrylates and alpha-substituted acrylates, such asmethacrylates. If a low molecular weight fluoropolymer is preferred,such polymers are prepared from the corresponding monomers as listedabove but include a chain transfer agent, e.g., alkanethiol, such asdodecyl mercaptan, to terminate the polymer. As illustrative of thefluoropolymers which may be used in the present invention, mention maybe made of the following:

Homopolymers of 1H, 1H perfluorohexyl acrylate 1H, 1H perfluorocetylacrylate 1H, 1H perfluorodecyl acrylate 1H, 1H perfluorododecyl acrylate1H, 1H perfluorohexyl methacrylate 1H, 1H perfluorodecyl methacrylate1H, 1H perfluorododecyl methacrylate 1H, 11-!perfluorodecyla-fluoroacrylate 1H, 1H 7H perfluoroheptyl acrylate 1H,1H, 1 1H perfluoroundecyl methacrylate 1H, 1H, 3H perfluoroacetylacrylate 1H, 1H perfluoroheptyla-chloroacrylate in the general formulaof which may be presented as follows:

wherein X is hydrogen, chlorine or fluorine; X is hydrogen, alkyl (C, toC chlorine or fluorine, n has a value of 3 to 30, m=l, 2 or 3. X ishydrogen, lower alkyl (C to C or halogen and at least 70 percent but notless than 6 of the X's are fluorine; interpolymers (i.e., copolymers andterpolymers of the aforementioned monomers; with polymerizable vinylcompounds, said interpolymer containing at least 25 mole percent offluoromonomer.

Suitable comonomers include: vinyl esters of organic and inorganicacids, e.g., vinyl chloride; vinyl bromide; vinyl fluoride; vinylacetate; vinyl propionate; vinyl stearate, vinyl benzoate;

. l N-methylol acrylamide; N-methoxy methyl acrylamide styrene, alkylstyrenes 1,3-butadiene alkyl esters alkyl halides monoand di-acrylateesters of alkanediols monoand di-vinyl esters of alkanedioic acids andthe like. Specific copolymers, terpolymers and interpolymers of par- (b)2. 0% n-butyl acrylate (c) 0.5% N-methylol acrylamide I (b) 50%2-ethy1hexyl methacrylate CH (u) 25% C Fa(C F2)5OH2CH2O IC=CH-r (b) 10%2-ethylhexyl methacrylate (c) 5% N-methylol acrylamide I (a) 80%CHF2(CF2)5CH2OGC=CH2 ll (b) 5% n-butyl acrylate (c) 10% Z-ethylhexylmethacrylate (d) 5% n-butyl methacrylate (b) 2% 2-ethy1hexylacrylate F I(a) 97.5% CF3(CF2) CH CH O?I C=CHz VII.

(b) 2% n-butyl acrylato (c) 0.5% N-methylol acrylamlde VIII. =CH:

ln lieu of the fluorohomopolymer or interpolymers described above, lowmolecular weight fluorohomopolymers 75 and fluorointerpolymers may beutilized. These are prepared by emulsion polymerization product isprepared C. for 5 hours).

X. CH3

2 parts N-butyl acrylate 2 parts octadecyl dimethylamine acetate 12parts dodecyl mercaptan 200 parts water The polymer produced by thistechnique is ofmuch lower molecular weight than that normally preparedin the absence of the chain transfer agent, dodecyl mercaptan.

The formulations of the present invention may be used in any convenientconcentration in a bath spray, roller padder or aerosol method ofapplication. Generally, concentrations are percent, wet pickup, theconcentrations of active components in the treating composition for thepreferred pickup will vary from about 40 down to 0.1 percent. Clearly,such concentragreat latitude indicated above.

ln the preferred and most convenient method of application by theconsumer of the composition of this invention, ie, aerosol method, theaqueous compositions are formulated witha suitable propellant. Theseinclude trichloromonofluoromethane, dichlorotetrafluoroethane,dichloromonofluoromethane, monochlorotrifluoromethane, isobutane,difluoroethane} n-butane, propane, 1,1,1- difluorochloroethane,l,l,l-cyclobutane, carbon dioxide, nitrous oxide.

In general, the propellants are water-immiscible or only slightlysoluble in water with vapor pressures at 70 F. of from about 0.2 toabout 500 p.s.i.g. The selection-of a suitable propellant or mixture ofpropellants will, of course, depend on the type of package to be used,the specific nature of the comothers. Where lower pressures are to bemaintained in the package it may be desirable to use a propellant ofslight water solubility to aid in dispensing the product after it leavesthe nozzle,

The preferred propellants are the low-density compounds and mixtures oflow density which form a separate and upper density, medium vaporpressure hydrocarbons such as isobutane are preferred.

In addition to the ethoxylated starch and fl uoropolymer there may alsobe present in the compositions of this invention many other additiveswhich do not adversely affect the attainment of stiffening andantisoiling (water and oil repellency). Examples of such additionalmaterials may include antistick agents such as the siloxane resins,polyethylene and the like; additional water repellent materials such aslong chain fatty quaternary ammonium compounds; antioxidants;antifoamers; bactericides; surface active agents; coloring materials,perfumes; textile fiber-reactive chemicals, e.g. formaldehyde, glyoxal;crease resistant and crease-proofing agents, and the like.

The following examples serve to illustrate the present invention withoutbeing deemed limitative thereof. Parts are by weight unless otherwiseindicated.

The starch is cooked up as a percent solution. The remaining formulawater is added, followed by the formalin, perfume and lastly thefluoropolymers. Concentrated ammonia is then added slowly to adjust thepH to 9.0:t0.l. The ironing aid is added followed by the sodiumbenzoate.

A sample of cotton fabric is immersed in the above aqueous compositionsqueezed to 50 percent pickup, air dried until slightly damp and ironedat 400 F. to dryness. The resultant fabric exhibits good waterandoil-repellency and has a crisp handle characteristic of a starchedmaterial.

EXAMPLE II Ninety-three percent of the alkaline aqueous formulation ofExample I was mixed with 7 percent isobutane propellant and packaged ina tin can. There was no evidence of corrosion or settling of componentingredients even after 5 days of standing at room temperature.

EXAMPLE Ill Aerosol Spray Fabric Size Ingredients 7: by WeightEthoxylated Corn Starch l.0

(same as Ex. I) Tcrpolymer of Ex. I L08 Copolymcr of Ex. I 0.36 Water.deionized 97.33 Concentrated ammonia 0.04 Ironing aid 0.05 Formalin 0.04Sodium Benzoate 0.10 Perfume 0.002

A 10 percent starch solution was cooked up. The rest of the water wasadded followed by the other ingredients. The ammonia was added to adjustthe pH to 9.1:01.

No precipitate nor change in pH was noted after standing at roomtemperature for 5 days.

EXAMPLE V Example IV is repeated wherein the propellant and amountthereof is varied as follows: (with a corresponding change in water)Isobutane 592 Isobutane 10% Isobutane 20% n-butanc 8'7: Freon l2 6%methyl chloride 4% hexafluoroethane 3% nitrous oxide 7 6% 4zl mixtureot'isobu taneand Freon l2 6% Excellent results are obtained.

As the above examples illustrate, the compositions of this inventionproduce excellent sizing along with unique waterand oil-repellency ontextiles. The compositions may be applied to the textiles in anyconvenient manner although they are most superior when used in anaerosol form. Where the propellant in these compositions is more densethan the aqueous components, the package structure will, obviously, varyfrom those packages or container used with propellants which are lessdense than and form an upper discrete liquid phase. Regardless of thesevariations, however, excellent properties are forthcoming in allinstances. I

Many substances may be added to the compositions of this invention, aspointed out above, and as will be obvious to one skilledin the art, theparameters are extremely varied, particularly in view of the fact thatnone of the additives need be soluble either in water or the selectedpropellant; Where it is desired, a compound may be added as a solutionin a suitable solvent and such solution added to the aqueouscompositions producing in most instances a dispersion of the saidcompound in the compositions. Many other variations will be apparent andit is clear that these may be resorted to without departing from thespirit and scope of this invention and that the specific embodiments setout herein are in no way limitative thereof.

What is claimed is:

1. A stable, antisoiling aqueous textile-treating composition comprisinga. ethoxylated starch having a molecular weight of from 30,000 to 50,000and containing from 0.05 to 0.08 mole of ethylene oxide, and

b. a thermoplastic the ratio of the solids of (a) to (b) ranging from3:1 to :1.

2. A composition as defined in claim 1, including a propellant, wherebysaid composition is rendered self-propellant.

3. A composition as defined in claim 2, wherein said propellant is alow-boiling material selected from the group consisting of hydrocarbons,halogenated hydrocarbons and mixtures thereof.

4. A composition as defined in claim 3, wherein the propellantconstitutes about 5 to 25 percent by weight of the composition. I

5. A composition as defined in claim 4, wherein the ethoxylated starchconstitutes about 1 to 10 percent by weight of the total composition.

6. A composition as defined in claim 1, wherein the ratio of starch tofluoropolymer component is 3:1.

7. A composition as defined in claim 4 wherein the amount of ethoxylatedstarch is 4 percent, the amount of perfluoro polymer is 1 percent andthe propellant is isobutane. 5

8. A composition as defined in claim 7 wherein the perfluoro polymer isa terpolymer.

2. A composition as defined in claim 1, including a propellant, wherebysaid composition is rendered self-propellant.
 3. A composition asdefined in claim 2, wherein said propellant is a low-boiling materialselected from the group consisting of hydrocarbons, halogenatedhydrocarbons and mixtures thereof.
 4. A composition as defined in claim3, wherein the propellant constitutes about 5 to 25 percent by weight ofthe composition.
 5. A composition as defined in claim 4, wherein theethoxylated starch constitutes about 1 to 10 percent by weight of thetotal composition.
 6. A composition as defined in claim 1, wherein theratio of starch to fluoropolymer component is 3:1.
 7. A composition asdefined in claim 4 wherein the amount of ethoxylated starch is 4percent, the amount of perfluoro polymer is 1 percent and the propellantis isobutane.
 8. A composition as defined in claim 7 wherein theperfluoro polymer is a terpolymer.